lithium 1-adamantoxide

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: lithium 1-adamantoxide
• 英文别名: Lithium;adamantan-1-olate
• 化学式: C₁₀H₁₅O*Li
• 分子量: 158.169
• InChiKey: ZBPRKOADIHMLIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.68
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  P-chloro-N-(2,4,6-tri-tert-butylphenyl)-λ³-iminophosphine 、 lithium 1-adamantoxide 生成 1-adamantyloxy-(2,4,6-tritert-butylphenyl)iminophosphane
  参考文献：
  名称：

  Markovsky, L. N.; Romanenko, V. D.; Ruban, A. V., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 329 - 332

  摘要：

  DOI：
• 作为产物：
  描述：

  1-金刚烷醇 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.25h， 生成 lithium 1-adamantoxide
  参考文献：
  名称：

  酰氟的克级制备及其与受阻亲核试剂的反应

  摘要：

  使用酰氯和氟化氢水溶液之间的相转移催化卤素交换，以 100 mmol 的规模合成了一系列酰氟。方便的程序包括在室温下剧烈搅拌双相混合物，然后萃取和蒸馏。分离的酰氟（通常为 7-20 g）显示出极好的纯度，并且在温和条件下用氨基锂碱和醇盐处理时可以转化为空间位阻酰胺和酯。

  DOI：

  10.1055/a-1649-5460

文献信息

• [EN] MESO-SELECTIVE SYNTHESIS OF ANSA-METALLOCENES<br/>[FR] SYNTHESE MESO-SELECTIVE D'ANSA-METALLOCENES
  申请人：BASELL POLYOLEFINE GMBH

  公开号：WO2005058929A1

  公开（公告）日：2005-06-30

  The present invention relates to a process for the meso-selective preparation of ansa-metallocene complexes of the formula (I), which comprises reacting a ligand starting compound of the formula (II) with a transition metal compound of the formula III, where R1, R1 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R2, R2 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R3 is a bulky organic radical which has at least 3 carbon atoms, is bound to the oxygen atom via a nonaromatic carbon or silicon atom and may be substituted by halogen atoms or further organic radicals having from 1 to 20 carbon atoms and may also contain heteroatoms selected from the group consisting of Si, N, P, O and S, T, T’ are identical or different and are each a divalent organic group which has from 1 to 40 carbon atoms and together with the cyclopentadienyl ring forms at least one further saturated or unsaturated, substituted or unsubstituted ring system having a ring size of from 5 to 12 atoms, where T and T’ may contain the heteroatoms Si, Ge, N, P, As, Sb, O, S, Se or Te within the ring system fused to the cyclopentadienyl ring, A is a bridge consisting of a divalent atom or a divalent group, M1 is an element of group 3, 4, 5 or 6 of the Periodic Table of the Elements or the lanthanides, the radicals X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion, x is a natural number from 1 to 4, M2 is an alkali metal, an alkaline earth metal or a magnesium monohalide fragment, p is 1 in the case of doubly positively charged metal ions or 2 in the case of singly positively charged metal ions or metal ion fragments, LB is an uncharged Lewis base ligand, and y is a natural number from 0 to 6, and also the subsequent reaction of these complexes to form ansa-metallocenes of the formula (IV), the use of transition metal compounds of the formula (III) for preparing metallocenes and also transition metal compounds of the formula (III), ansa-metallocene complexes of the formula (I) and the use of these as constituents of catalyst systems for the polymerization of olefines.

  本发明涉及一种制备式(I)的中间体选择性的ansa-金属茂配合物的方法，该方法包括将式(II)的配体起始化合物与式(III)的过渡金属化合物反应，其中R1，R1相同或不同，均为氢或具有1至40个碳原子的有机基团，R2，R2相同或不同，均为氢或具有1至40个碳原子的有机基团，R3是一个笨重的有机基团，它至少有3个碳原子，通过非芳香碳或硅原子与氧原子结合，并且可以被卤素原子或具有1至20个碳原子的进一步有机基团取代，并且还可以包含从Si，N，P，O和S的选择的杂原子中选择的杂原子，T，T'相同或不同，均为具有1至40个碳原子的二价有机基团，并且与环戊二烯基环一起形成至少一个具有5至12个原子的饱和或不饱和、取代或未取代的环系统，其中T和T'可以在融合到环戊二烯基环的环系统中包含杂原子Si，Ge，N，P，As，Sb，O，S，Se或Te，A是由二价原子或二价基团构成的桥，M1是元素3、4、5或6的周期表或镧系元素中的一个，基团X相同或不同，均为有机或无机基团，能够被环戊二烯基阴离子取代，x是1至4的自然数，M2是碱金属、碱土金属或镁单卤化物片段，p在二价阳离子金属离子的情况下为1，在单价阳离子金属离子或金属离子片段的情况下为2，LB是一个无电荷的路易斯碱配体，y是0至6的自然数，以及这些配合物的后续反应形成式(IV)的ansa-金属茂，使用式(III)的过渡金属化合物制备金属茂，以及式(III)的过渡金属化合物，式(I)的ansa-金属茂配合物，以及将它们用作催化剂体系的组分，用于烯烃的聚合。
• Portability of the RNNMo(3+) core — Application to the synthesis of dinitrogen-derived trialkoxymolybdenum organodiazenido complexes
  作者：John-Paul F Cherry、Paula L Diaconescu、Christopher C Cummins

  DOI：10.1139/v05-025

  日期：2005.4.1

  An alcoholysis strategy has been employed in the synthesis of new oligo- or polymeric trialkoxymolybdenum diazenido complexes [R¹NNMo(O-1-Ad)₃]_x (R¹ = Me or C(O)OMe) as well as their mononuclear THF solvates R¹NNMo(O-1-Ad)₃(THF). Dinitrogen-derived diazenido precursor complexes R¹NNMo(N[R]Ar)₃ (R = i-Pr, Ar = 3,5-C₆H₃Me₂) react smoothly with 3 equiv. 1-adamantanol to liberate 3 equiv. HN(R)Ar without disruption of the diazenidomolybdenum(3+) core. X-ray structural investigations were carried out for diazenido complex MeNNMo(O-1-Ad)₃(THF) and for the corresponding cationic dimethyldiazenido complex [Me₂NNMo(O-1-Ad)₃(THF)]⁺, obtained as its triflate salt. The latter cation was found upon cobaltocene reduction to undergo N—N bond cleavage, producing nitride NMo(O-1-Ad)₃ (synthesized independently) and dimethylamine. Key words: molybdenum, dinitrogen, bond cleavage, hydrazido, diazenido.

  在新的寡聚或聚合三烷氧基钼联氮化物[R1NNMo(O-1-Ad)3]x（其中R1 = Me或C（O）OMe）的合成中，采用了一种醇解策略，以及它们的单核THF溶剂R1NNMo（O-1-Ad）3（THF）。 Dinitrogen衍生的联氮化物前体[R1NNMo（N [R] Ar）3]（其中R = i-Pr，Ar = 3,5-C6H3Me2）与3当量的1-金刚烷醇反应，以释放3当量的HN（R）Ar，而不破坏联氮化钼（3+）核。对于联氮化物MeNNMo（O-1-Ad）3（THF）以及相应的阳离子二甲基联氮化物配合物[Me2NNMo（O-1-Ad）3（THF）] +（以其三氟甲磺酸盐的形式获得）进行了X射线结构研究。后者的阳离子在钴二茂铁还原时被发现经历了N-N键断裂，产生硝化物NMo（O-1-Ad）3（独立合成）和二甲胺。关键词：钼，二氮化物，键断裂，肼基，联氮化物。
• Gram-Scale Preparation of Acyl Fluorides and Their Reactions with Hindered Nucleophiles
  作者：Michał Barbasiewicz、Michał Tryniszewski

  DOI：10.1055/a-1649-5460

  日期：2022.3

  A series of acyl fluorides was synthesized at 100 mmol scale using phase-transfer-catalyzed halogen exchange between acyl chlorides and aqueous bifluoride solution. The convenient procedure consists of vigorous stirring of the biphasic mixture at room temperature, followed by extraction and distillation. Isolated acyl fluorides (usually 7–20 g) display excellent purity and can be transformed into sterically

  使用酰氯和氟化氢水溶液之间的相转移催化卤素交换，以 100 mmol 的规模合成了一系列酰氟。方便的程序包括在室温下剧烈搅拌双相混合物，然后萃取和蒸馏。分离的酰氟（通常为 7-20 g）显示出极好的纯度，并且在温和条件下用氨基锂碱和醇盐处理时可以转化为空间位阻酰胺和酯。
• Markovsky, L. N.; Romanenko, V. D.; Ruban, A. V., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 49/50, p. 329 - 332
  作者：Markovsky, L. N.、Romanenko, V. D.、Ruban, A. V.、Drapailo, A. B.、Reitel, G. V.、Sarina, T. V.

  DOI：——

  日期：——